JPH0466225B2 - - Google Patents
Info
- Publication number
- JPH0466225B2 JPH0466225B2 JP59134387A JP13438784A JPH0466225B2 JP H0466225 B2 JPH0466225 B2 JP H0466225B2 JP 59134387 A JP59134387 A JP 59134387A JP 13438784 A JP13438784 A JP 13438784A JP H0466225 B2 JPH0466225 B2 JP H0466225B2
- Authority
- JP
- Japan
- Prior art keywords
- halogenated
- nitrobenzoic acid
- represented
- dichloro
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000005338 nitrobenzoic acids Chemical class 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 5
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- -1 2,3,4-trichloro-6-nitrobenzoic acid Chemical compound 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- JSEVUBOYVADSHX-UHFFFAOYSA-N 1,3-dichloro-2-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(F)=C1Cl JSEVUBOYVADSHX-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- MTBYTWZDRVOMBR-UHFFFAOYSA-N 1,2,3,4-tetrachloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C(Cl)=C1Cl MTBYTWZDRVOMBR-UHFFFAOYSA-N 0.000 description 1
- BGKIECJVXXHLDP-UHFFFAOYSA-N 1,2,3-trichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1Cl BGKIECJVXXHLDP-UHFFFAOYSA-N 0.000 description 1
- HHLCSFGOTLUREE-UHFFFAOYSA-N 1,2,3-trichloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C(Cl)=C1 HHLCSFGOTLUREE-UHFFFAOYSA-N 0.000 description 1
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 description 1
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- OWALCRQILZGQDH-UHFFFAOYSA-N 1,3-dichloro-2,4-difluoro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(F)C(Cl)=C1F OWALCRQILZGQDH-UHFFFAOYSA-N 0.000 description 1
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- XNJAYQHWXYJBBD-UHFFFAOYSA-N 1,4-difluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(F)=CC=C1F XNJAYQHWXYJBBD-UHFFFAOYSA-N 0.000 description 1
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 1
- QUIMTLZDMCNYGY-UHFFFAOYSA-N 2,4-dichloro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1Cl QUIMTLZDMCNYGY-UHFFFAOYSA-N 0.000 description 1
- RJXOVESYJFXCGI-UHFFFAOYSA-N 2,4-difluoro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1F RJXOVESYJFXCGI-UHFFFAOYSA-N 0.000 description 1
- OPOMBXSGXKFMGY-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Br)C(Cl)=C1 OPOMBXSGXKFMGY-UHFFFAOYSA-N 0.000 description 1
- DPHCXXYPSYMICK-UHFFFAOYSA-N 2-chloro-1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(Cl)=C1 DPHCXXYPSYMICK-UHFFFAOYSA-N 0.000 description 1
- KSLPTAKLPKUBES-UHFFFAOYSA-N 3,4,5-trichloro-2-nitrobenzoic acid Chemical compound ClC=1C(=C(C(=C(C(=O)O)C1)[N+](=O)[O-])Cl)Cl KSLPTAKLPKUBES-UHFFFAOYSA-N 0.000 description 1
- ZWJZUUYLXVXJSF-UHFFFAOYSA-N 3,4-dichloro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(Cl)=C1[N+]([O-])=O ZWJZUUYLXVXJSF-UHFFFAOYSA-N 0.000 description 1
- LKMJMYZOEGSMDN-UHFFFAOYSA-N 3,5-dichloro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=CC(Cl)=C1[N+]([O-])=O LKMJMYZOEGSMDN-UHFFFAOYSA-N 0.000 description 1
- ZBEWIPTYUHHZIS-UHFFFAOYSA-N 3,5-difluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=CC(F)=C1[N+]([O-])=O ZBEWIPTYUHHZIS-UHFFFAOYSA-N 0.000 description 1
- TVKAWNFBYDPGGW-UHFFFAOYSA-N 3,6-difluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=C(F)C=CC(F)=C1[N+]([O-])=O TVKAWNFBYDPGGW-UHFFFAOYSA-N 0.000 description 1
- SUHYJVCHLDIPIY-UHFFFAOYSA-N 4,5-dichloro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=C(Cl)C=C1[N+]([O-])=O SUHYJVCHLDIPIY-UHFFFAOYSA-N 0.000 description 1
- QWRNVDWDFCINEY-UHFFFAOYSA-N 4-bromo-2-chloro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1Cl QWRNVDWDFCINEY-UHFFFAOYSA-N 0.000 description 1
- GGTQVIUWLUDQKR-UHFFFAOYSA-N 4-chloro-5-fluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(Cl)C=C1[N+]([O-])=O GGTQVIUWLUDQKR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
「発明の目的」
〔産業上の利用分野〕
本発明は、特開昭57−46986号公報に示される
ピリド〔１，２，３−de〕〔１，４〕ベンゾオキ
サジン誘導体等をはじめとする抗菌剤の製造中間
体として有用なハロゲン化ニトロベンゼン類の工
業的製造方法に関する。Detailed Description of the Invention "Object of the Invention" [Industrial Application Field] The present invention relates to the use of pyrido[1,2,3-de][1,4]benzo This invention relates to an industrial method for producing halogenated nitrobenzenes useful as intermediates for producing antibacterial agents such as oxazine derivatives.
従来、脱炭酸反応によるハロゲン化ニトロベン
ゼン類の選択的製造方法としては、銅粉又は酸化
銅の存在下キノリン中で加熱脱炭酸反応させる方
法が知られている。（ケミカル・アブストラクト
ラフト第74巻64020記載）
〔発明が解決しようとする問題点〕
しかしながら、前記方法では収率が最高60％と
低くさらに高収率でハロゲン化ニトロベンゼン類
を工業的に製造する方法が望まれていた。
Conventionally, as a method for selectively producing halogenated nitrobenzenes by decarboxylation, a method of carrying out a heating decarboxylation reaction in quinoline in the presence of copper powder or copper oxide is known. (Chemical Abstracts Volume 74, 64020) [Problems to be Solved by the Invention] However, in the above method, the yield is as low as 60% at most, and there is no method for industrially producing halogenated nitrobenzenes with an even higher yield. was desired.
「発明の構成」
〔問題点を解決するための手段、作用〕
本発明者らはこのような現状に鑑み、ハロゲン
化ニトロベンゼン類の工業的製造方法を提供すべ
く鋭意研究を重ねた結果、以外にも有機溶媒とし
て非プロトン性極性溶媒を、触媒として三級アミ
ン類、アルカリ金属の炭酸塩及び炭酸水素塩から
なる群より選ばれた化合物をそれぞれ選択使用し
これらの存在下ハロゲン化ニトロ安息香酸類を加
熱脱炭酸反応させることにより、従来の問題点を
解決し得ることを見出し本発明を成すに至つた。"Structure of the Invention" [Means and effects for solving the problem] In view of the current situation, the present inventors have conducted extensive research to provide an industrial method for producing halogenated nitrobenzenes, and as a result, have discovered the following. In addition, an aprotic polar solvent was used as the organic solvent, and a compound selected from the group consisting of tertiary amines, alkali metal carbonates, and hydrogen carbonates was used as the catalyst, and halogenated nitrobenzoic acids were treated in the presence of these. The present inventors have discovered that the problems of the prior art can be solved by carrying out a heating decarboxylation reaction.
すなわち本発明は有機溶媒中、一般式
（式中X1，X2，X3，及びX4は、水素原子もし
くはハロゲン原子を示し、各々が同一又は異なつ
てもよい。ただし、３者又は４者が同時に水素原
子であることはない。）
で表されるハロゲン化ニトロ安息香酸類を加熱脱
炭酸反応させて、一般式
（式中X1，X2，X3，及びX4は前記と同様の意
味を有する。）
で表されるハロゲン化ニトロベンゼン類を製造す
る方法において、有機溶媒として非プロトン性極
性溶媒を、触媒として三級アミン類、アルカリ金
属の炭酸塩及び炭酸水素塩からなる群より選ばれ
た化合物をそれぞれ選択使用することを特徴とす
る前記一般式（）で示されるハロゲン化ニトロ
ベンゼン類の製造方法である。 That is, the present invention provides the method for preparing the general formula in an organic solvent. (In the formula, X 1 , X 2 , X 3 , and X 4 represent hydrogen atoms or halogen atoms, and each may be the same or different. However, three or four of them cannot be hydrogen atoms at the same time. ) The halogenated nitrobenzoic acids represented by (In the formula, X 1 , X 2 , X 3 and X 4 have the same meanings as above.) In the method for producing halogenated nitrobenzenes represented by A method for producing halogenated nitrobenzenes represented by the general formula (), which comprises selectively using compounds selected from the group consisting of tertiary amines, alkali metal carbonates, and hydrogen carbonates. .
本発明において原料として使用するハロゲン化
ニトロ安息香酸は一般式（）で示される化合物
であり、例えば３，４−ジクロロ−２−ニトロ安
息香酸、３，５−ジクロロ−２−ニトロ安息香
酸、４，５−ジクロロ−２−ニトロ安息香酸、
３，４，５−トリクロロ−２−ニトロ安息香酸、
２，３，４−トリクロロ−６−ニトロ安息香酸、
２，３，４，５−テトラクロロ−６−ニトロ安息
香酸、３，５−ジクロロ−４−フルオロ−２−ニ
トロ安息香酸、３，５−ジフルオロ−２−ニトロ
安息香酸、５−ブロモ−３−クロロ−２−ニトロ
安息香酸、３，６−ジフルオロ−２−ニトロ安息
香酸、４−クロロ−５−フルオロ−２−ニトロ安
息香酸、２，４−ジフルオロ−３−ブロモ−６−
ニトロ安息香酸、３，５−ジフルオロ−４，６−
ジクロロ−２−ニトロ安息香酸等を挙げることが
できる。 The halogenated nitrobenzoic acid used as a raw material in the present invention is a compound represented by the general formula (), such as 3,4-dichloro-2-nitrobenzoic acid, 3,5-dichloro-2-nitrobenzoic acid, 4 , 5-dichloro-2-nitrobenzoic acid,
3,4,5-trichloro-2-nitrobenzoic acid,
2,3,4-trichloro-6-nitrobenzoic acid,
2,3,4,5-tetrachloro-6-nitrobenzoic acid, 3,5-dichloro-4-fluoro-2-nitrobenzoic acid, 3,5-difluoro-2-nitrobenzoic acid, 5-bromo-3 -Chloro-2-nitrobenzoic acid, 3,6-difluoro-2-nitrobenzoic acid, 4-chloro-5-fluoro-2-nitrobenzoic acid, 2,4-difluoro-3-bromo-6-
Nitrobenzoic acid, 3,5-difluoro-4,6-
Dichloro-2-nitrobenzoic acid and the like can be mentioned.
本発明で使用する触媒は、三級アミン類又はア
ルカリ金属の炭酸塩及び炭酸水素塩からなる群よ
り選ばれた化合物であるが、具体的に例えば、ト
リエチルアミン、トリプロピルアミンなどの三級
アミン類、炭酸ナトリウム、炭酸カリウム、炭酸
リチウムなどの炭酸塩、炭酸水素ナトリウム、炭
酸水素カリウムなどの炭酸水素塩が挙げられる。
尚、塩化ナトリウム等のハロゲン化アルカリ金属
塩を使用した場合、目的物を高収率で得ることは
できない。 The catalyst used in the present invention is a compound selected from the group consisting of tertiary amines or alkali metal carbonates and hydrogen carbonates, and specifically includes tertiary amines such as triethylamine and tripropylamine. , carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, and hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate.
Note that when an alkali metal halide salt such as sodium chloride is used, the desired product cannot be obtained in high yield.
また、非プロトン性極性溶媒としてはジメチル
ホルムアミド、ジメチルスルホキシド、ジメチル
アセトアミド、ジグライム、スルホラン、１，３
−ジメチル−２−イミダゾリノン、ジメチルスル
ホン、ニトロベンゼン等が挙げられる。尚、キノ
リン、キシレン等の非プロトン性極性溶媒以外の
溶媒を用いた場合は目的の化合物が得られない。 In addition, examples of aprotic polar solvents include dimethylformamide, dimethylsulfoxide, dimethylacetamide, diglyme, sulfolane, 1,3
-dimethyl-2-imidazolinone, dimethylsulfone, nitrobenzene and the like. Note that if a solvent other than an aprotic polar solvent such as quinoline or xylene is used, the desired compound cannot be obtained.
本発明においてハロゲン化ニトロ安息香酸類を
脱炭酸させて得られるハロゲン化ニトロベンゼン
類は、一般式（）で示される化合物であり、例
えば２，３−ジクロロニトロベンゼン、２，４−
ジクロロニトロベンゼン、３，４−ジクロロニト
ロベンゼン、２，３，４−トリクロロニトロベン
ゼン、３，４，５−トリクロロニトロベンゼン、
２，３，４，５−テトラクロロニトロベンゼン、
２，４−ジクロロ−３−フルオロニトロベンゼ
ン、２，４−ジフルオロニトロベンゼン、２−ク
ロロ−４−ブロモニトロベンゼン、２，５−ジフ
ルオロニトロベンゼン、３−クロロ−４−フルオ
ロニトロベンゼン、３，５−ジクロロ−４−ブロ
モニトロベンゼン、２，４−ジフルオロ−３，５
−ジクロロニトロベンゼン等を挙げることができ
る。 In the present invention, halogenated nitrobenzenes obtained by decarboxylating halogenated nitrobenzoic acids are compounds represented by the general formula (), such as 2,3-dichloronitrobenzene, 2,4-
Dichloronitrobenzene, 3,4-dichloronitrobenzene, 2,3,4-trichloronitrobenzene, 3,4,5-trichloronitrobenzene,
2,3,4,5-tetrachloronitrobenzene,
2,4-dichloro-3-fluoronitrobenzene, 2,4-difluoronitrobenzene, 2-chloro-4-bromonitrobenzene, 2,5-difluoronitrobenzene, 3-chloro-4-fluoronitrobenzene, 3,5-dichloro-4 -bromonitrobenzene, 2,4-difluoro-3,5
-dichloronitrobenzene and the like.
本発明の方法は非プロトン性極性溶媒、一般式
（）で示されるハロゲン化ニトロ安息香酸及び
ハロゲン化ニトロ安息香酸１モル当り0.01モル以
上、好ましくは、0.05〜0.5モルの触媒を混合し
て100〜200℃、好ましくは130〜180℃で0.2〜５
時間撹拌し脱炭酸反応させることにより行われ
る。得られた反応液から溶媒を減圧留去し残渣を
水中にあけた後、有機溶媒を加え常法により抽
出、濃縮、蒸留することによつて一般式（）で
示されるハロゲン化ニトロベンゼン類が高純度、
高収率で得られる。 The method of the present invention involves mixing an aprotic polar solvent, a halogenated nitrobenzoic acid represented by the general formula (), and a catalyst of 0.01 mole or more, preferably 0.05 to 0.5 mole, per mole of the halogenated nitrobenzoic acid. 0.2-5 at ~200℃, preferably 130-180℃
This is carried out by stirring for a period of time and causing a decarboxylation reaction. The solvent was distilled off from the resulting reaction solution under reduced pressure and the residue was poured into water, followed by addition of an organic solvent and extraction, concentration, and distillation in a conventional manner to obtain a highly halogenated nitrobenzene represented by the general formula (). purity,
Obtained in high yield.
以下、実施例により本発明をさらに具体的に説
明する。
Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
１４径フラスコにジメチルアセトアミド500
mlと炭酸ナトリウム8.12ｇ（0.0766mol）を加え、
135〜140℃に昇温し、３，５−ジクロロ−４−フ
ルオロ−２−ニトロ安息香酸97.4ｇ（0.383mol）
を加え、同温度で2.5時間撹拌下反応させた。得
られた反応液から溶媒を減圧留去し残渣を水中に
あけた後、トルエンにより抽出後、濃縮、蒸留す
ることにより２，４−ジクロロ−３−フルオロニ
トロベンゼン77.2ｇ（bp.123〜125℃／10mmＨｇ）
を得た、収率は96.0％であつた。Example 1 Dimethylacetamide 500 in a 14-diameter flask
ml and 8.12g (0.0766mol) of sodium carbonate,
The temperature was raised to 135-140°C, and 97.4 g (0.383 mol) of 3,5-dichloro-4-fluoro-2-nitrobenzoic acid
was added and reacted at the same temperature for 2.5 hours with stirring. The solvent was distilled off from the resulting reaction solution under reduced pressure, the residue was poured into water, extracted with toluene, concentrated and distilled to yield 77.2 g of 2,4-dichloro-3-fluoronitrobenzene (bp. 123-125°C). /10mmHg)
The yield was 96.0%.
比較例 １
ジメチルアセトアミドの代わりにキシレンを用
いた以外は、実施例１と同様に行つたところ反応
は進行せず、目的とする２，４−ジクロロ−３−
フルオロニトロベンゼンは得られなかつた。Comparative Example 1 The same procedure as in Example 1 was carried out except that xylene was used instead of dimethylacetamide, but the reaction did not proceed and the desired 2,4-dichloro-3-
No fluoronitrobenzene was obtained.
比較例 ２
触媒の炭酸ナトリウムを除いた以外は、実施例
１と同様に行つたところ、目的とする２，４−ジ
クロロ−３−フルオロニトロベンゼンの収量は３
時間後で18.3ｇ（収率22.7％）であつた。Comparative Example 2 The same procedure as in Example 1 was carried out except that the sodium carbonate catalyst was omitted, and the yield of the target 2,4-dichloro-3-fluoronitrobenzene was 3.
After hours, the amount was 18.3 g (yield 22.7%).
比較例 ３
触媒として塩化ナトリウム4.50ｇ（0.077mol）
を用いた以外は、実施例１と同様に行つたとこ
ろ、目的とする２，４−ジクロロ−３−フルオロ
ニトロベンゼンの収量は３時間後で16.8ｇ（収率
20.9％）、５時間後で28.8ｇ（収率35.8％）であつ
た。Comparative example 3 Sodium chloride 4.50g (0.077mol) as a catalyst
The procedure was carried out in the same manner as in Example 1, except for using
20.9%) and 28.8g (yield 35.8%) after 5 hours.
「発明の効果」
本発明の方法は、有機溶媒として非プロトン性
極性溶媒を、触媒として三級アミン類、アルカリ
金属の炭酸塩及び炭酸水素塩からなる群より選ば
れた化合物を、それぞれ選択使用することによつ
て、従来法に比べ高収率でハロゲン化ニトロベン
ゼン類が得られ、しかも排水処理に及ぼす影響も
ないなど工業的に優れた製造方法である。"Effects of the Invention" The method of the present invention selectively uses an aprotic polar solvent as an organic solvent and a compound selected from the group consisting of tertiary amines, alkali metal carbonates, and hydrogen carbonates as a catalyst. By doing so, halogenated nitrobenzenes can be obtained in higher yields than conventional methods, and it has no effect on wastewater treatment, making it an industrially superior production method.
Claims (1)
くはハロゲン原子を示し、各々が同一又は異なつ
てもよい。ただし、３者又は４者が同時に水素原
子であることはない。） で表されるハロゲン化ニトロ安息香酸類を加熱脱
炭酸反応させて、一般式 （式中X1，X2，X3，及びX4は前記と同様の意
味を有する。） で表されるハロゲン化ニトロベンゼン類を製造す
る方法において、有機溶媒として非プロトン性極
性溶媒を、触媒として三級アミン類、アルカリ金
属の炭酸塩及び炭酸水素塩からなる群より選ばれ
た化合物をそれぞれ選択使用することを特徴とす
る前記一般式（）で示されるハロゲン化ニトロ
ベンゼン類の製造方法。[Claims] 1. In an organic solvent, the general formula (In the formula, X 1 , X 2 , X 3 , and X 4 represent hydrogen atoms or halogen atoms, and each may be the same or different. However, three or four of them cannot be hydrogen atoms at the same time. ) The halogenated nitrobenzoic acids represented by (In the formula, X 1 , X 2 , X 3 and X 4 have the same meanings as above.) In the method for producing halogenated nitrobenzenes represented by A method for producing halogenated nitrobenzenes represented by the general formula (), characterized in that a compound selected from the group consisting of tertiary amines, alkali metal carbonates, and hydrogen carbonates is used as the compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59134387A JPS6112650A (en) | 1984-06-29 | 1984-06-29 | Production of halogenated nitrobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59134387A JPS6112650A (en) | 1984-06-29 | 1984-06-29 | Production of halogenated nitrobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6112650A JPS6112650A (en) | 1986-01-21 |
| JPH0466225B2 true JPH0466225B2 (en) | 1992-10-22 |
Family
ID=15127205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59134387A Granted JPS6112650A (en) | 1984-06-29 | 1984-06-29 | Production of halogenated nitrobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6112650A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL119290A (en) * | 1995-09-26 | 2001-01-11 | Nippon Catalytic Chem Ind | Method for production of benzene halides |
-
1984
- 1984-06-29 JP JP59134387A patent/JPS6112650A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6112650A (en) | 1986-01-21 |
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